JPH07324110A - New alternating copolymer - Google Patents

Abstract

PURPOSE:To obtain an alternating copolymer comprising recurring units represented by a given formula wherein structural units (I) represented by a specific formula are linked alternately with structural units (II) represented by a specific formula. CONSTITUTION:An isopentenyl compd. such as methylbutenyl ether and an unsatd. compd. such as maleic anhydride mixed together at a predetermined proportion are polymerized in the presence of a radical initiator such as azoisobutyronitrile. After completion of the reaction, the, resulting product is purified with a reprecipiting solvent to obtain an alternating copolymer having an average mol.wt. of 3,000 to 300,000 and comprising recurring units of the formula IV or V wherein structural units (I) of the formula I (wherein R<1> as an alkyl, cycloalkyl, aryl or aralkyl group having an ether bond) are linked alternately with structural units (II) of the formula II (wherein R<2> is COOR<4> or is combined with R<3> to form -COXCO-; R<4> and R<6> are each alkyl; X is NR<5> or O; and R<5> is H, alkyl, phenyl, or the like) or the formula III (wherein R<7> is cyano or COOR<9>; R<9> is alkyl; and R<8> as H, Cl, F, or cyano).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an alternating copolymer containing an isopentenyl compound as a constituent.

[0002]

2. Description of the Related Art Since the carbon-carbon double bond of an isopentenyl compound has low reactivity and does not polymerize alone by radical polymerization, there has been almost no study of polymerization of this compound. An example of emulsion copolymerization of isopentenyl alcohol or prenyl alcohol and unsaturated carboxylic acid or its salt is disclosed in JP-A-59-108.
No. 010 and JP-A No. 59-102496.

[0003]

The copolymer obtained by the above-mentioned known method has a composition ratio of isopentenyl alcohol or prenyl alcohol of 15 to 33 mol%,
It is hard to say that it is an alternating copolymer. An object of the present invention is to provide a novel alternating copolymer having an isopentenyl compound as a constituent.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that an isopentenyl compound, which is said to have extremely low reactivity, causes extremely efficient alternating copolymerization with a specific unsaturated compound at a ratio of 1: 1. Has reached the present invention. That is, according to the present invention, the following general formula (A)

[0005]

[Chemical 8]

(Wherein R ¹ represents an alkyl group optionally having an ether bond, a cycloalkyl group, an aryl group or an aralkyl group) and a structural unit [I] represented by the following general formula (B) or (C)

[0007]

[Chemical 9]

Wherein R ² represents --COOR ⁴ or together with R ³ forms --COXCO--, wherein R ⁴ represents an alkyl group, X represents NR ⁵ or O, and R ⁵ Is a hydrogen atom, an alkyl group, a phenyl group,

[0009]

[Chemical 10]

Or

[0011]

[Chemical 11]

Represents R ³ represents a -COOR ^6,
Here, R ⁶ represents an alkyl group. )

[0013]

[Chemical 12]

(In the formula, R ⁷ is a cyano group or —COOR ⁹
Wherein R ⁹ represents an alkyl group. R ⁸ represents a hydrogen atom, a chlorine atom, a fluorine atom or a cyano group. ) And a structural unit [II] represented by the following formula (i) or (ii) in which these structural units [I] and [II] are alternately linked.

[0015]

[Chemical 13]

[0016]

[Chemical 14]

(Wherein R ¹ , R ² , R ³ , R ⁷ and R ⁸ have the same meanings as defined above) and have an average molecular weight of 3,000 to 300,000. A copolymer is provided.

In the above general formula (A), R ¹ represents an alkyl group which may have an ether bond, a cycloalkyl group, an aryl group or an aralkyl group. As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group,
A pentyl group, a hexyl group, etc. are mentioned, C1-C6
Are preferred. Examples of the alkyl group which may have an ether bond include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a propoxymethyl group, a proxyethyl group, a putoxymethyl group, a butoxyethyl group, a pentoxymethyl group and a pen. Examples thereof include a toxyethyl group, an isopentenoxymethyl group and an isopentenoxyethyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like. Benzyl group as the aralkyl group, 1
-Phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group and the like are exemplified.

Examples of the compound providing the structural unit [I] represented by the general formula (A) include methylprenyl ether, ethylprenyl ether, propylprenyl ether, butylprenyl ether, amylprenyl ether, isoamylprenyl ether, hexylprenyl ether, Examples include ethers such as cyclohexylprenyl ether, cyclopentylprenyl ether, benzylprenyl and phenylprenyl.

Further, in the present invention, as the unsaturated compound which gives the structural unit [II] represented by the general formula (B) or (C), maleic anhydride; maleimide, N-methylmaleimide, N-ethylmaleimide, N- Maleimides such as phenylcarboxylic acid maleimide, N-propyl maleimide, N-butyl maleimide, N-phenyl maleimide, N-phenyl sulfonic acid maleimide; dimethyl maleate, diethyl maleate, dipropyl maleate,
Dialkyl maleates such as dibutyl maleate, dihexyl maleate and dioctyl maleate; dimethyl fumarate, diethyl fumarate, dipropyl fumarate,
Dialkyl fumarates such as dibutyl fumarate, dihexyl fumarate, dioctyl fumarate; methyl acrylate, ethyl acrylate, propyl acrylate, methyl 2-chloroacrylate, methyl 2-fluoroacrylate, 2
-Acrylic esters such as ethyl fluoroacrylate; acrylonitrile, 2-chloroacrylonitrile,
Unsaturated nitriles such as 2-cyanoacrylonitrile may be mentioned.

The average molecular weight of the alternating copolymer of the present invention is about 3,000 to 300,000.

The copolymerization reaction of the isopentenyl compound and the unsaturated compound can be carried out according to a known method. Examples thereof include solution polymerization in an organic solvent, emulsion polymerization in water, suspension polymerization of Ken, and the like; or solution polymerization in a mixed solvent of a water-soluble organic solvent and water, suspension polymerization, emulsion polymerization, and the like. Further, by utilizing the property that an isopentenyl compound does not polymerize alone, solution polymerization using this compound as a monomer / solvent can be mentioned. From the viewpoint of reactivity, reaction operation, separation operation of the reaction mixture, etc., it is preferable to use the isopentenyl compound in excess as a solvent. In the copolymerization reaction, a radical initiator such as an azo compound or an organic peroxide is used as a polymerization initiator in an organic solvent or in a solution polymerization system using an isopentenyl compound as a solvent. Also, for the polymerization system in water, persulfate,
Hydrogen peroxide or the like is used. Upon polymerization in a mixed solvent of a water-soluble organic solvent and water, a combination of the above various polymerization initiators can be appropriately selected and used. The polymerization temperature is not particularly limited, but it is preferable to select a temperature at which the decomposition of the polymerization initiator occurs promptly.

The fact that a 1: 1 alternating copolymer was obtained by the above reaction means that the copolymerization composition was 1: regardless of the mixing ratio of each component.
It is confirmed to be 1 by elemental analysis value, infrared absorption spectrum, nuclear magnetic resonance spectrum and the like.

Since the alternating copolymer of the present invention is soluble in an organic solvent and has a hydroxyl group, an ester group, an acid anhydride group, etc., it may be used alone or in addition to the secondary crosslinking reaction. It is possible to cause intramolecular or intermolecular reactions using these chemicals. In particular, since the alternating copolymer containing maleic anhydride as a structural unit has a highly reactive acid anhydride group in the molecule, a nucleophilic functional group such as a hydroxyl group, an amino group, a mercapto group, an epoxy group or an isocyanate group. It can easily react with a compound having a metal to form a covalent bond or can form an ionic bond with various metal ion compounds. The alternating copolymer of the present invention may have various functions depending on the combination of the structural unit [I] represented by the general formula (A) and the structural unit [II] represented by the general formula (B) or (C). Therefore, polymer carrier, polymer surface treatment material, super water absorbent resin, ion exchange resin, medical material, antifogging agent, scale inhibitor, dispersant, adhesive, sizing agent,
It can be applied to separation membrane materials, electronic materials, resist materials and the like.

[0025]

The present invention will be described in more detail with reference to the following examples. In the examples, the molecular weight is the weight average molecular weight (M
w). Mw and Mw / Mn are calculated from the results based on the GPC method using polystyrene as a standard substance, and the copolymerization composition ratio is calculated from ¹ H-NMR data.

Example 1 Azobisisobutyronitrile (0.06 mol% based on maleic anhydride) was used as an initiator with methylprenyl ether and maleic anhydride under the conditions shown in Table 1, and the temperature was 65 ° C. for 5 hours. Polymerization was carried out. As the polymerization proceeded, the produced polymer precipitated in powder form. After completion of the reaction, the reaction mixture was added to the reprecipitation solvent to precipitate the polymer. Table of the obtained results
1 and i. r. And n. m. r. The measurement results of are shown in Table-2.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

According to the present invention, there is provided a novel alternating copolymer having an isopentenyl compound as a constituent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08F 222/14 MMH 222/40 MNE MNF

Claims (1)

[Claims] 1. The following general formula (A): (In the formula, R ¹ represents an alkyl group which may have an ether bond, a cycloalkyl group, an aryl group or an aralkyl group) and a structural unit [I] represented by the following general formula (B) or (C) [Chemical 2] (In the formula, R ² represents -COOR ⁴ or forms -COXCO- together with R ³ , wherein R ⁴ represents an alkyl group, X represents NR ⁵ or O, and R ⁵ represents a hydrogen atom. ,
Alkyl group, phenyl group, Or Represents R ³ represents a -COOR ^6, wherein R ⁶ represents an alkyl group. ) [Chemical 5] (In the formula, R ⁷ represents a cyano group or —COOR ⁹ , where R ⁹ represents an alkyl group, and R ⁸ represents a hydrogen atom, a chlorine atom, a fluorine atom or a cyano group.) II] and the structural units [I] and [II] are alternately connected to each other, and the following formula (i) or (ii): [Chemical 7] (In the above formula, R ¹ , R ² , R ³ , R ⁷ and R ⁸ are as defined above.) An alternating copolymer having a repeating unit and an average molecular weight of 3,000 to 300,000. .